Organosilicate polymer and insulating film therefrom

ABSTRACT

The present invention relates to a low dielectric substance essential for a next generating electrical device such as a semiconductor device having high performance and high density, and particularly to a process for preparing a low dielectric organosilicate polymer, a hydrolysis condensation product of a carbon-bridged oligomer; a process for manufacturing an insulating film using an organosilicate polymer prepared by the process; and an electrical device comprising an insulating film prepared by the process. The organosilicate polymer prepared according the process of the present invention is thermally stable, and has good film-forming prosperities, excellent mechanical strength and crack resistance, and the film manufactured therefrom has excellent insulating properties, film uniformity, dielectric properties, crack resistance, and mechanical strength.

This application is the national phase under 35 U.S.C. §371 of PCTInternational Application No. PCT/KR02/00888 which has an Internationalfiling date of May 13, 2002, which designated the United States ofAmerica.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

The present invention relates to low dielectric materials essential fora next generation electric device such as a semiconductor device, with ahigh density and high performance. More specifically, the presentinvention relates to a process for preparing an organosilicate polymerthat is thermally stable and has good film-forming properties andexcellent mechanical strength and crack resistance, and a process formanufacturing an insulating film using an organosilicate polymerprepared by the process.

(b) Description of the Related Art

The semiconductor industry is moving toward increasing devicecomplexity, requiring shrinking geometric dimensions and highercomponent integration with greater dimensional densities in integratedcircuit devices, e.g. memory and logic chips. This has led to anincrease in the number of wiring levels and a reduction in wiring pitchto increase the wiring density. Current leading-edge logic processorshave 7˜8 levels of high density interconnect, and interconnect linewidths are scheduled to decrease to 0.1 μm around the year 2004.

As device dimensions shrink to less than 0.25 μm, propagation delay,crosstalk noise, and power dissipation due to resistance-capacitance(RC) coupling become significant. The smaller line dimension increasesthe resistivity of metal wires, and the narrow intermetal spacingincreases the capacitance between the metal wires. Thus, although theswitching speed of devices will increase as the feature size decreases,the interconnect delay becomes the major fraction of the total delay andlimits the overall chip performance. Accordingly, in order to prepare achip having high speed, a conductor having a low resistance and adielectric material having a low dielectric constant should be used. Inaddition, the use of low dielectric material can remarkably decrease thepower dissipation and crosstalk noise.

Recently, several semiconductor device manufacturers have put testproducts on the market that show improvements in their performance of20% or more, using copper wiring with high electric conductivity insteadof using the conventional aluminum wiring. A shift to use of newmaterials that exhibit low dielectric constant performance, for use ininterconnects, has recently been undertaken. If the dielectric filmsbetween interconnect layers in integrated circuits can make use of thesematerials, the effect on operating speed will be the same as that whichresulted with the switch from aluminum to copper technology. Forinstance, if the dielectric constant of the dielectric material ischanged from 4.0 to about 2.5, IC operating speed will be improved byabout 20%.

The interlayer dielectric material used in semiconductor integratedcircuit devices is predominantly SiO₂, which is generally formed usingchemical vapor deposition (CVD) to withstand various processingoperations associated with the conditions under which a dielectric isformed. The dielectric constant of silicon thermal oxidation films,which have the lowest dielectric constant, is on the order of 4.0.Attempts have been made to reduce the dielectric constant by introducingfluorine atoms into an inorganic film deposited by CVD. However, theintroduction of fluorine atoms in large amounts decreases the chemicaland thermal stability, so the dielectric constant achieved in actualpractice is on the order of 3.5. Fluorinated oxides can provide animmediate near-term solution, and a shift to new types of insulatingmaterials with sub-3 dielectric constant may be required.

One class of candidates is organic polymers, some of which have adielectric constant of less than 3.0. Incorporating fluorine into suchorganic polymers is known to further lower the dielectric constant. Mostorganic polymers do not, however, posses the physico-chemical propertiesrequired for on-chip semiconductor insulation, particularly thermalstability and mechanical properties (sufficient to withstand back-endline fabrication temperatures within the range of 400˜450° C.). Feworganic polymers are stable at temperature greater than 450° C. Theyalso have a low glass transition temperature and thus elasticity thereofremarkably decreases at high temperatures, and they have a very highlinear expansion coefficient. Since the temperature rises to 450° C.during semiconductor IC integration and packaging processes, theresulting low thermal stability and elasticity and high linear expansioncoefficient can deteriorate the reliability of the devices.

Recently, in order to solve thermal stability problems of organicpolymers, the development of organic silicate polymers using a sol-gelprocess has emerged. In particular, organic SOG (Spin On Glass), havinga dielectric constant in the range of about 2.7˜3.3, has been proposedfor use as interlayer dielectrics in which the side chain of an organiccomponent (an alky group such as methyl) is bonded to the backbond chainof a siloxane bond. However, the organosilicate polymers show poormechanical properties. For instance, polymethylsilsesquioxane showscrack formation during processing unless the film is very thin (often <1μm), and shows low mechanical modulus due to the introduction of thealkyl group.

Miller et al. have reported a method of toughening the silsesquioxanematerial systems by incorporating a small amount of a polymericsubstituents such as a polyimide. A method of mixing an inorganic fineparticulate powder is known as a method for improving the mechanicalstrength of organosilicates. Although various systems have beenproposed, there remains a need for a material having a suitable lowdielectric constant and appropriate physico-chemical properties for useas an interlayer dielectric in the future generation of IC devices.

SUMMARY OF THE INVENTION

Accordingly, the present invention is made in consideration of theproblems of the prior art, and it is an object of the present inventionto provide a process for preparing a low dielectric material for a verylow dielectric interlayer wiring insulating film that can make the speedof a semiconductor device high, decrease power consumption, andremarkably decrease cross-talk between metal wiring.

It is another object of the present invention to provide a process forpreparing an organosilicate polymer having excellent crack resistance,mechanical strength, film-forming properties, and dielectric properties,and a process for manufacturing an insulating film containing thepolymer prepared according to the process.

In order to achieve these objects, the present invention provides twokinds of processes for preparing an organosilicate polymer.

The first process comprises:

a) providing an organometallic silane compound represented by thefollowing Chemical Formula 1;

b) causing a Grignard reaction of the a) organometallic silane compoundrepresented by the Chemical Formula 1 alone to prepare a carbon-bridgedsilane oligomer and removing metallic compound by-products; and

c) mixing the b) carbon-bridged silaneoligomer in organic solvent, andadding water and a catalyst thereto to cause hydrolysis and condensationto prepare an organosilicate polymer.R¹ _(p)R² _(3−p)SiR³MX  [Chemical Formula 1]wherein

R¹ is independently hydrogen, fluorine, aryl, vinyl, allyl, orfluorine-substituted or unsubstituted linear or branched C₁-₄ alkyl;

R² is independently chlorine, acetoxy, hydroxy, or linear or branchedC₁-₄ alkoxy;

R³ is C₁-₆ hydrocarbon;

M is magnesium, mercury, or copper;

X is halogen; and

p is an integer of 0 to 2.

In addition, the second process comprises:

a) providing an organometallic silane compound represented by the aboveChemical Formula 1;

b) causing a Grignard reaction of

i) the a) organometallic silane compound represented by the ChemicalFormula 1; and

ii) a silane compound or silane oligomer to prepare a carbon-bridgedsilane oligomer and removing metallic compound by-products; and

c) mixing the b) carbon-bridged silaneoligomer in organic solvent, andadding water and a catalyst thereto to cause hydrolysis and condensationto prepare an organosilicate polymer.

The present invention also provides a composition for forming asemiconductor device insulating film comprising an organosilicatepolymer prepared by one of the above processes, and a process formanufacturing an insulating film for a semiconductor device comprisingcoating and curing the composition.

Specifically, the composition for forming a semiconductor deviceinsulating film of the present invention comprises

a) an organosilicate polymer prepared by each organosilicate polymerpreparation process; and

b) an organic solvent.

The composition for forming an insulating film may further comprise

c) one or more kinds of additives selected from a group consisting oforganic molecules, organic polymer, organic dendrimer, colloidal silica,aerosol, xerosol, and surfactant.

The present invention also provides a process for manufacturing aninsulating film for a semiconductor device, comprising

-   -   a) providing an organosilicate polymer prepared by each        organosilicate polymer preparation process;    -   b) dissolving the organosilicate polymer and, if necessary, an        additive in a solvent;    -   c) coating the organosilicate polymer solution on a        semiconductor device substrate; and    -   d) drying and curing the coated insulating film, and a        semiconductor device comprising an insulating film prepared by        the process.

DETAILED DESCRIPTION AND THE PREFERRED EMBODIMENTS

The present invention will now be explained in more detail.

According to the present invention, a bridged organosilane oligomer isprepared from an organometallic silane compound represented by thefollowing Chemical Formula 1, and an organosilicate polymer is preparedtherefrom. The present invention provides a composition for forming aninsulating film comprising the organosilicate polymer, a process formanufacturing an insulating film for a semiconductor device comprisingthe organosilicate polymer, and a semiconductor device comprising theinsulating film.

The organosilicate polymer prepared according to the present invention,if applied to an insulating film for a semiconductor device, hasexcellent insulating properties, film uniformity, dielectric properties,crack resistance, and mechanical strength.

The following equations are examples of the organosilicate preparationprocess of the present invention.

The first preparation process accompanies the following Equation 1.

As shown, a Grignard reaction of the organometallic silane compound ofthe Chemical Formula 1 alone prepares a carbon-bridged silane oligomer,wherein metallic compound by-products are removed. The carbon-bridgedsilane oligomer is dissolved in an organic solvent, and water and acatalyst are added thereto to cause hydrolysis and condensation toprepare an organosilicate polymer. Also, the carbon-bridged silaneoligomer and a silane compound or silane oligomer are mixed in anorganic solvent, and water and a catalyst are added thereto to causehydrolysis and condensation to prepare an organosilicate polymer.

The second process accompanies the following Equation 2.

The Grignard reaction between the organometallic silane compound of theChemical Formula 1 and a silane compound or silane oligomer prepares acarbon-bridged silane oligomer. The carbon-bridged silane oligomer isdissolved in an organic solvent, and water and a catalyst are addedthereto to cause hydrolysis and condensation to prepare anorganosilicate polymer. Also the carbon-bridged silane oligomer and asilane compound or silane oligomer are then mixed in an organic solvent,and water and a catalyst are added thereto to cause hydrolysis andcondensation to prepare an organosilicate polymer.

Raw material for preparing the organosilicate polymer of the presentinvention is an organometallic silane compound satisfying the ChemicalFormula 1. The organometallic silane compound is preferably prepared by

a) introducing metal into a reaction vessel and drying it; and

b) adding an organic solvent and silane compound represented by thefollowing Chemical Formula 2 into the vessel to react them to prepare anorganometallic silane compound satisfying the above Chemical Formula 1.R¹ _(p)R² _(3−p)SiR³X  [Chemical Formula 2](wherein

R¹ is independently hydrogen, fluorine, aryl, vinyl, allyl, orfluorine-substituted or unsubstituted linear or branched C₁-₄ alkyl;

R² is independently chlorine, acetoxy, hydroxy, or linear or branchedC₁-₄ alkoxy;

R³ is C₁-₆ hydrocarbon;

X is halogen; and

p is an integer of 0 to 2.

The reaction between metal and organosilane compound, for example,accompanies the following Equation 3.

Namely, chloroalkylsilane, an organosilane compound satisfying the aboveChemical Formula 2, is reacted with metal Mg to prepare one of theorganometallic silane compounds satisfying the Chemical Formula 1.

The silane compound used in said process for preparing thecarbon-bridged silane oligomer or final product organosilicate polymerincludes an organic silane monomer comprising silicon, carbon, oxygen,and hydrogen, and organic silane oligomers that can be preparedtherefrom. Preferably, a silane compound represented by the followingChemical Formula 3 or an oligomer thereof can be used to prepared thecarbon-bridged silane oligomer or final product organosilicate polymer.R⁴ _(q)R⁵ _(4−q)Si  [Chemical Formula 3](wherein

R⁴ is independently hydrogen, fluorine, aryl, vinyl, allyl, orfluorine-substituted or unsubstituted linear or branched C₁-₄ alkyl;

R⁵ is independently chlorine, acetoxy, hydroxy, or linear or branchedC₁-₄ alkoxy; and

q is an integer of 0 to 3.)

According to the present invention, the carbon-bridged silane oligomerand silane compound or silane oligomer are hydrolyzed and condensed inthe presence of a solvent while adding water and a catalyst to obtain anorganosilicate polymer with a specific molecular weight, and hence acomposition for forming an insulating film.

Sovents used for hydrolysis and condensation or for film coating includeany agent or mixture of agents that will dissolve the composition toform a homogeneous liquid mixture of a silane compound or a silaneoligomer and the carbon-bridged silane oligomer. The solvent used in thepresent invention includes, as examples, aliphatic hydrocarbons such asn-pentane, i-pentane, n-hexane, i-hexane, 2,2,4-trimethylpentane,cyclohexane, methylcyclohexane, etc.; aromatic hydrocarbons such asbenzene, toluene, xylene, trimethylbenzene, ethylbenzene,methylethylbenzene, etc.; alcohols such as methylalcohol, ethylalcohol,n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol,cyclohexanol, methylcyclohexanol, glycerol, etc.; ethers such astetrahydrofuran, 2-methyl tetrahydrofuran, ethylether, n-propylether,isopropylether, diglyme, dioxane, dimethyl dio ethyleneglycolmonomethylether, ethyleneglycol dimethylether, ethyleneglycoldiethylether, propyleneglycol monomethylether, propyleneglycoldimethylether, etc.; esters such as diethylcarbonate, methylacetate,ethylacetate, ethyllactate; ethyleneglycol monomethylether acetate,propyleneglycol monomethylether acetate, ethylglycol diacetate, etc.;and amides such as N-methylpyrrolidone, formamide, N-methylformamide,N-ethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, etc.

All the solvents used in hydrolysis and condensation are removed afterthe reaction to obtain an organosilicate polymer oil or powder, and theorganosilicate polymer can be dissolved in an organic solvent forforming a film or the organic solvent used in hydrolysis andcondensation can be directly used to form a film. It is possible to usetwo or more kinds of the organic solvents together.

The present invention uses a catalyst in order to promote hydrolysis andcondensation. The catalyst used in hydrolysis and condensation includesan acid catalyst, a base catalyst, a metal chelate compound, a saltcatalyst, etc. For examples, the acid catalyst includes hydrochloricacid, nitric acid, sulfuric acid, phosphoric acid, formic acid,benzenesulfonic acid, toluene sulfonic acid, acetic acid, oxalic acid,malonic acid, maleic acid, fumaric acid, citric acid, propionic acid,etc.; and the base catalyst includes ammonia, sodium hydroxide, calciumhydroxide, potassium hydroxide, trimethylamine, triethylamine,diethanolamine, triethanolamine, dimethyl ethylalcohol amine, monomethyldiethanol aminediazabicycloundecene, pyridine, pyrrolpiperidine,choline, pyrrolidine, piperazine, etc. The metal chelate compoundincludes an organometallic compound comprising metals such as aluminum,titan, zirconium, tin, tantalum, etc.; and the salt catalyst includes aconjugate acid, and a conjugate base compound such as ammonium acetate.The acid, base, metal chelate compound, and salt catalysts can be usedalone or in combination, and two or more kinds thereof can be used bystage.

The amount of catalyst added can be any amount that facilitates thehydrolysis and condensation reaction of the bridged silane oligomer andsilane compound or silane oligomer, and the optimal amount will dependupon the chemical composition of the catalyst as well as the temperatureunder which the hydrolysis and condensation reaction occur. Generallythe catalyst is added in an amount of 0.00001 to 1 moles, preferably 0.5moles or less, per 1 mole of silicon atoms in the silane compound. Ifthe added contents of the catalyst exceeds 1 mole per 1 mole of siliconatoms in the silane compound, the reaction rate will be very high and itwill be difficult to control the molecular weight and gel may be easilyproduced.

In the present invention, water is added to cause hydrolysis of thesilane compound. The amount of water is suitably 0.1 to 20 moles,preferably 1 to 10 moles per 1 mole of silicon atoms in the silanecompound, and it can be added by stage or continuously. The catalyst maybe previously added to an organic solvent, or it can be dissolved ordispersed when adding water.

There are no particular limitations on the reaction temperature when theproduct is made to have a desired molecular weight. The temperature maypreferably be not higher than the boiling point of the organic solventused, and may preferably be 0° C. to 100° C. in order to control themolecular weight of the resultant hydrolyzed product. There are nolimitations on the reaction time at the time of hydrolysis andcondensation, and the reaction may be completed at the time the productreaches a stated molecular weight. It is usually preferred to set themolecular weight of the final product within a range of from 500 to1,000,000 as a weight-average molecular weight to form a uniform coatingfilm.

The present invention's coating composition for forming an insulatingfilm is prepared by dissolving the organisilicate polymers made by theabove processes with organic solvents. If desired, various additives,such as organic molecules, organic polymer, organic dendrimers,colloidal silica, aerosol, xerosol, surfactants, etc. can be added tothe composition for forming a certain amount of insulating filmaccording to its purpose.

The solid content concentration in the solution may suitably be selectedfrom the viewpoint of the desired viscosity of the solution or thethickness of the coating film, within the range whereby the solidcontent dissolves. In general the solid concentration of the compositionof the present invention is in the range of 2 to 60 wt %, preferably 5to 40 wt %.

The insulating film of the present invention is formed by coating theinsulating film composition on a substrate such as silicon wafer, SiO₂wafer, SiN wafer, semiconductor compound, etc. The insulating film canbe formed by standard processes such as spin-coating, flow coating, dipcoating, and spray coating. When the composition of the presentinvention is applied to an interlayer dielectric film for asemiconductor device, a spin coating method is preferred, since thein-plane distribution of the film thickness will thereby be uniform.

The thickness of the film can be controlled by changing the viscosity ofthe composition and the rotation speed of a spin coater, and for aninterlayer insulating film for a multilayered circuit for asemiconductor device, 0.2 to 2 μm is suitable.

An organosilicate polymer insulating film with a three dimensionalstructure can be formed through drying and curing (hardening) processesafter the coating process. Commonly, the drying and curing are performedrespectively at 30 to 250° C. and 300 to 600° C., and particularly thecuring is preferably performed at 350 to 500° C. If a curing temperatureexceeds 600° C., thermal stability of an organosilicate polymer willdecrease, and if it is less than 300° C., the strength of a film willdecrease because condensation polymerization of an organosilicatepolymer does not completely occur and dielectric properties mightdecrease due to the presence of residual functional groups.

The drying and curing processes can be continuously performed whileelevating the temperature at a specific rate, or they can be performedby stage. If performed by stage, the drying and curing processes aresuitably performed for 1 minute and 5 hours, respectively. Heating canbe performed using a hot plate, oven, furnace, etc., under an inert gasatmosphere such as with nitrogen or argon, a helium atmosphere, anoxygen atmosphere such as with an oxygen-containing gas (for example,air), a vacuum, or under an ammonium and hydrogen-containing gasatmosphere. The drying and curing can be performed by the same heatingmethod or by different heating methods.

After the curing processes, if necessary, surface treatment can beperformed by a common method in order to minimize the amount of hydroxygroups inside the insulating film. The surface treatment is done toremove residual hydroxy groups by impregnating the insulating film in asilane compound solution such as hexamethyldisilazane,alkylchlorosilane, and alkylacetoxysilane to cause a reactiontherebetween and drying it, or by heating the insulating film under areducing gas atmosphere such as a hydrogen or fluorine-containing gasatmosphere at 300 to 600° C. for 1 minute or more.

The film obtained by the process is suitably used for an interlayerinsulating film for a semiconductor device for LSI, system LSI, DRAM,SDRAM, D-RDRAM, etc.; a protection film such as surface coating film fora semiconductor device; an interlayer insulating film for a multilayeredwiring substrate; and a protection film or an insulation-preventing filmfor a liquid display device, because it has excellent insulatingproperties, film uniformity, dielectric properties, crack resistance,and mechanical strength.

The present invention will now be explained in more detail withreference to the following Examples and Comparative Examples. However,these Examples are to illustrate the present invention, and the presentinvention is not limited thereto.

EXAMPLE Example 1 Preparation of Organometallic Silane CompoundRepresented by the Chemical Formula 1

After introducing 0.71 g of magnesium in a reaction vessel and dryingit, 15 ml of solvent-distilled tetrahydrofuran (THF) were added thereto.The temperature of the mixture was lowered to 0° C., and 5 g ofchloromethyl triethoxy silane, an organosilane compound satisfying theChemical Formula 2, were slowly added to react until a Grignard reagentwas made and the reaction was confirmed by NMR.

Preparation of Carbon-Bridged Oligomer

After the initial reaction was completed, reaction was continued for 12hours to form a carbon-bridged oligomer. 50 ml of hexane were then addedthereto to precipitate magnesium salts and the precipitates werefiltered with celite, and then organic solvent was completely removed ina vacuum oven to obtain a product.

Preparation of Organosilicate Polymer

1.5 g of the obtained product and 4.64 g of methyltrimethoxysilane, anorganosilane compound satisfying the Chemical Formula 3, were mixed in11.3 ml of tetrahydrofuran solvent.

The temperature of the mixture was lowered to 0° C., and 1.78 ml ofdistilled water and 0.21 ml of a catalyst, 2 N hydrochloric acid, wereslowly added thereto to react for 30 minutes. Then, the temperature wasslowly elevated to 80° C. and the reaction was continued for 16 hourswhile heat-refluxing. After the reaction, the mixture was diluted withdiethylether solvent and washed with distilled water 3 to 4 times untilacidity became neutral. Remaining solvents were completely removed fromthe obtained organic layer in a vacuum oven to obtain a solid (powder)product.

Preparation of an Insulating Film

300 mg of the obtained powder were dissolved in methylisobutyl ketone toset a total weight of solution to 1.5 g. Impurities were removed fromthe obtained solution through a filter and the solution was spin-coatedto obtain a thin film. An insulating film was prepared through dryingand curing processes, elevating the temperature to 430° C. at a rate of2° C. per minute and maintaining the temperature for 1 hour under anitrogen atmosphere.

Example 2 Preparation of an Organometallic Silane Compound Representedby the Chemical Formula 1

After introducing 0.71 g of magnesium into a reaction vessel and dryingit, 15 ml of solvent-distilled tetrahydrofuran(THF) were added thereto.The temperature of the mixture was lowered to 0° C., and 0.2 g ofdichloromethane and 0.2 g of chloromethyl triethoxysilane, anorganosilane compound satisfying the Chemical Formula 2, were slowlyadded thereto. When a Grignard reagent began to be produced, 4.8 g ofchloromethyl triethoxysilane, an organic compound satisfying theChemical Formula 2, were further slowly added to prepare a Grignardreagent, and the reaction was confirmed by NMR.

Preparation of Carbon-Bridged Oligomer

5.37 g of tetramethoxy silane, a compound satisfying the ChemicalFormula 3, and 15 ml of tetrahydrofuran were slowly added to the abovesolution and the mixture was agitated at 0° C. for 2 hours. 50 mL ofhexane were added thereto to precipitate magnesium salts, and theprecipitates were filtered with celite. Organic solvents were thencompletely removed therefrom in a vacuum oven to obtain a carbon-bridgedsilane oligomer product.

Preparation of an Organosilicate Polymer

44.2 g of the obtained carbon-bridged silane oligomer and 18.17 g ofmethyltrimethoxysilane, an organosilane compound satisfying the ChemicalFormula 3, were mixed in 30 ml of tetrahydrofuran solvent.

The temperature of the mixture was lowered to 0° C., and 8.0 ml ofdistilled water and 0.98 ml of a catalyst, 5 N hydrochloric acid, wereslowly added thereto to react for 30 minutes. Then, the temperature wasslowly elevated to 80° C. and reaction was continued for 16 hours whileheat-refluxing. After the reaction, the mixture was distilled withdiethylether solvent and washed with distilled water 3 to 4 times untilthe acidity became neutral. Remaining solvents were completely removedfrom the obtained organic layer in a vacuum oven to obtain a solid(powder) product.

Preparation of an Insulating Film

The obtained powder was dried and cured by the same method as in Example1, to prepare an insulating film.

Example 3 Preparation of Organosilicate Polymer

9 g of the carbon-bridged oligomer obtained by the same method as inExample 1, 30.0 g of methyltrimethoxy silane, and 3.4 g oftetramethoxysilane were mixed in 60 ml of tetrahydrofuran solvent.

The temperature of the mixture was lowered to 0° C., and 37 ml of acatalyst, 0.01 N nitric acid, were slowly added thereto to react for 30minutes. Then, the temperature was slowly elevated to 70° C. and thereaction was continued for 16 hours while heat-refluxing. Afterreaction, the mixture was diluted with diethylether solvent and washedwith distilled water 3 to 4 times until acidity became neutral.Remaining solvents were completely removed from the obtained organiclayer in a vacuum oven to obtain a solid content.

Preparation of an Insulating Film

The obtained powder was dried and cured by the same method as in Example1, to prepare an insulating film.

Comparative Example 1

7.26 g of methyltrimethoxy silane, an organosilane compound, and 4.05 mlof distilled water were mixed in 10 ml of tetrahydrofuran (THF) solvent,and 0.80 ml of 2 N hydrochloric acid were slowly added thereto under anitrogen atmosphere.

After reacting them for 30 minutes at room temperature, the temperaturewas slowly increased and reaction was continued for 24 hours whileheat-refluxing.

After the reaction, the temperature of the solution was lowered to roomtemperature, and the solution was diluted with diethylether solvent andwashed with water 3 to 4 times until the acidity became neutral.Magnesium sulfate was introduced into the obtained organic layer tocompletely remove remaining water therefrom. Solvents were completelyremoved from the obtained organic layer in a vacuum oven to obtain asolid (powder) product.

Preparation of an Insulating Film

The obtained powder was dried and hardened by the same method as inExample 1 to prepare an insulating film.

Physical properties of the organosilicate polymer prepared in Examples1, 2, 3 and Comparative Example 1 were measured by the following methodsa)-c) to obtain the results shown in Table 1.

-   -   a) Molecular Weight (Mass average molecular weight: Mw)−Relative        molecular weight value was obtained by Gel Permeation        Chromatography (GPC) using a polystyrene as a standard.    -   b) Mechanical Properties of Thin Film—Measured after        spin-coating on 2×2 inch Si wafer and hardening at 430° C. for 1        hour under N₂ atmosphere.

i) Hardness—Measured using TriboIndenter from Hysitron Inc.

ii) Crack Resistance—A 1 μm thin film was prepared to observe whethercracks occurred.

-   -   c) Dielectric Properties of Film—A MIM        (metal/insulator/semiconductor) device was manufactured on a Si        wafer and dielectric properties were measured at 1 MHz using an        LCR meter from HP Company.

Results are shown in Table 1.

TABLE 1 Comparative Example 1 Example 2 Example 3 Example 1 Mw 1180727716 3100 11000 Hardness 0.62 0.58 1.1 0.32 Crack Resistance 2.4E125.3E−12 1.2E−12 1.3E−9 Dielectric Constant 2.78 2.75 2.83 2.73

As shown in Table 1, a thin film manufactured from the organosilicatepolymer of the present invention has good dielectric properties andimproved mechanical strength and crack resistance.

The organosilicate polymer prepared according to the present inventionis thermally stable and has good film-forming properties, excellentmechanical strength and crack resistance, and the film manufacturedtherefrom has excellent insulating properties, film uniformity,dielectric properties, crack resistance, and mechanical strength.

1. A composition for forming an insulating film for a semiconductordevice, comprising a) an organosilicate polymer prepared by a processcomprising the steps of i) providing an organometallic silane compoundrepresented by Chemical Formula 1 below; ii) causing a Grignard reactionof the i) organometallic silane compound alone, or the i) organometallicsilane compound and a silane compound or silane oligomer to prepare acarbon-bridged silane oligomer and remove metal compound by products;and iii) mixing the ii) carbon-bridged silane oligomer in organicsolvent, and adding water and a catalyst thereto to cause hydrolysis andcondensation to prepare an organosilicate polymer; and b) an organicsolvent:R¹ _(p)R² _(3−p)SiR³MX  Chemical Formula 1 wherein R¹ is independentlyhydrogen, fluorine, aryl, vinyl, allyl, or fluorine substituted orunsubstituted linear or branched C₁₋₄ alkyl; R² is independentlychlorine, acetoxy, hydroxy, or linear or branched C₁₋₄ alkoxy; R³ isC₁₋₆ hydrocarbon; M is magnesium, mercury, or copper; X is halogen; andp is an integer of 0 to
 2. 2. The composition for forming an insulatingfilm according to claim 1, further comprising, c) one or more additivesselected from the group consisting of organic molecules, organicpolymer, organic dendrimer, colloidal silica, aerosol, xerosol, andsurfactant.
 3. A process for manufacturing an insulating film for asemiconductor device, comprising the steps of: a) coating thecomposition of claim 1 on a substrate of a semiconductor device toprepare a coated insulating film and b) drying and curing the coatedinsulating film.
 4. The process for manufacturing an insulating filmaccording to claim 3, wherein the a) composition further comprises oneor more additives selected from the group consisting of organicmolecules, organic polymer, organic dendrimer, colloidal silica,aerosol, xerosol, and surfactant.
 5. A semiconductor device comprisingan insulating film prepared according to the process of claim 3.